CN101930189B - Purified polyester resins for toner performance improvement - Google Patents

Abstract

The invention discloses a purified polyester resin for toner performance improvement. A toner that includes at least one polyester resin wherein the amount of free polyvalent acid monomer in the polyester resin is less than 4 mg/gram, and wherein the percentage of the at least one polyester resin with a Mw less than 1500 is less than about 10%.

Description

Can improve the purified polyester resins of toner performance

Technical field

The developer that is used to form and shows image that the application's disclosure relates to colorant and comprises this colorant, in particular to the colorant forming with purified polyester resins.The application's disclosure also relates to the method for producing and using described colorant and developer.

Background technology

In electrophotographic printing method, the photoreceptor that comprises photoconductive insulation course on conductive layer is by making static electrification lotus and the imaging equably of described conductive layer surface.For example, by making photoreceptor be subject to a kind of activate electromagnetic radiation (light) and irradiating, disperse the electric charge in the irradiation area of described photoconductive insulation course this radiation-selective, and form electrostatic latent image on non-irradiated region.Thereby pigment granules attracted to formation colorant sub-image on sub-image from carrier granular.Then this toner image is transferred to paper and is fused on paper from described photo-conductive surface.

Use many adjuvants and constituent to produce the multiple colorant composition for this class print system.Conventionally, pigment granules constituent comprises such as resin of jointing material, and for example colorant of any adjuvant and wax, thereby makes described pigment granules have special properties.

Plurality of devices and method are used to prepare pigment granules.The example of commercial known method comprises that the melt blending of colorant component in Banbury roller mill equipment, spraying are dry, dispersin polymerization, solution polymerization etc.The another kind of equipment and the method that can be used for preparing colorant composition are to melt extrude equipment and method, and its relative Banbury roller mill equipment and method have multiple advantages.For example, melt extruding is continuity method instead of batch method, and extrusion method can easily realize robotization, makes to carry out more economical colorant preparation.United States Patent (USP) 4,894,308,4,973,439,5,145,762,5,227,460,5,376,494 and 5,468,586 have described the example of the conventional colorant of producing by extrusion by melting, and described document is included in herein by reference in full.

Emulsion aggregation colorant is also the excellent colorant that is used to form printed matter and/or xeroprinting image, because this class colorant can be made into even size and is environmental protection.The United States Patent (USP) of describing emulsion aggregation colorant comprises for example United States Patent (USP) 5, 370, 963, 5, 418, 108, 5, 290, 654, 5, 278, 020, 5, 308, 734, 5, 344, 738, 5, 403, 693, 5, 364, 729, 5, 346, 797, 5, 348, 832, 5, 405, 728, 5, 366, 841, 5, 496, 676, 5, 527, 658, 5, 585, 215, 5, 650, 255, 5, 650, 256, 5, 501, 935, 5, 723, 253, 5, 744, 520, 5, 763, 133, 5, 766, 818, 5, 747, 215, 5, 827, 633, 5, 853, 944, 5, 804, 349, 5, 840, 462 and 5, 869, 215, described document is included in herein by reference in full.

Emulsion aggregation technology generally includes the latex by resin being heated or formed by using emulsion polymerization to prepare latex in water---if necessary optionally together with solvent---resin particle in water, the diameter of described resin particle is less, for example from approximately 5 to approximately 500 nanometers.For example by Pigments, the disperse system in water is to form separately to colorant disperse system, and it is optionally also separately added with resin.Colorant disperse system is added in latex potpourri, and then add polycoagulant or complexing agent to form the pigment granules of assembling.By the pigment granules heating of assembling so that its coalescence/melting, thereby obtain assembling, the pigment granules of fusion.

Known two kinds of main emulsion aggregation colorants.The first is the emulsion aggregation method that forms acrylic ester type pigment granules (for example styrene-acrylate pigment granules).As an example of these class methods, referring to for example U.S. Patent No. 6,120,967, the document is included in herein by reference in full.The second is emulsion aggregation (EA) method that forms polyester pigment granules (for example sodium sulfonate polyester pigment granules).As an example of these class methods, referring to for example U.S. Patent No. 5,916,725, the document is included in herein by reference in full.Or, pigment granules can form by the EA method that has used prefabricated polyester latex emulsion, described polyester latex emulsion is to use solvent evaporates or phase conversion emulsifying to make, those colorant methods of for example describing in U.S. Patent Application Publication text No.2008/0236446, the document is included in herein by reference in full.In addition, so-called ultralow molten polyester colorant can be by adding suitable crystal polyester to obtain.The example of the ultralow melting of EA (ULM) polyester colorant is for example U.S. Patent No. 5,057,392,5,147,747,6,383,705,6,780,557,6,942,951,7,056,635 and U.S. Patent Application Publication text No.2008/0236446 in describe those, described document is included in herein in full by reference.

Because polyester-type colorant can be realized lower minimum fixed temperature (MFT), polyester-type colorant (the polyester-type colorant that routine is extruded and the polyester-type colorant of assembling based on emulsification) has started to substitute cinnamic acrylic ester colorant recently.The colorant that MFT is lower can provide higher printing capability and/or lower fusion temperature and therefore reduce printing energy consumption.Polyester can be prepared by the progressively growth polycondensation of diacid and glycol.For obtaining high molecular weight polyesters by polycondensation reaction, conventionally require high temperature and need vacuum to remove alcohol accessory substance.Along with the increase of molecular weight of polyesters, its viscosity also sharply increases.This viscosity increase can cause process control inaccurate, and therefore the molecular weight distribution of gained polyester is conventionally very wide.The example of ultralow melting (ULM) colorant has for example U.S. Patent No. 4,246,332,4,980,448,5,156,937,5,202,212,5,830,979,5,902,709 and 6,335,139, and in U.S. Patent Application Publication text No.2007/0248903, describe those, these colorants are prepared by several different methods, described document is included in herein in full by reference.

Although the colorant being made up of these resins can show excellent melting property, comprise lower broken line MFT and wider fusion range, but existing problems still, for example colorant poor fluidity, colorant stop up that temperature electrification by friction susceptibility lower, that change for humidity is high and the printer fusion device life-span is short.The inventor thinks, these problems may be owing to existing a large amount of low molecular weight material to cause in vibrin.Low molecular weight material in vibrin is made up of the short chain oligomer of diacid and dihydroxy monomer and these monomers conventionally.The volatilization in a large number under the hot conditions relevant with described fusion device conventionally of these low molecular weight material, thus cause in described fusing apparatus situ generation adverse chemical reaction.For example, under hot conditions, carry out image fixing during, free polybasic acids monomer (unconverted monomer) can with fusion device oil and/or colorant in some additive reaction, generation can be deposited on the pollutant on fusion device roller, for example zinc salt pollutant.The quantity of gathering remarkable minimizing electrostatic printing apparatus exportable zero defect printed matter before needs are changed fusion device roller of these pollutants.The inventor also thinks, thereby the problem such as colorant poor fluidity and stopping up may easily plastify pigment granules and cause colorant Tg (glass transition temperature) to reduce relevant with pollutant.In addition, the existence of low-molecular-weight acid monomers and oligomer is considered to can cause more easily absorbing moisture, thus the variable charging performance that impact changes with ambient humidity level.

Summary of the invention

Thereby still need the amount of low molecular weight material to reduce the colorant of the variation minimum of the residue molecular weight distribution that makes resin, described colorant has multiple advantages, for example electrification by friction is more stable, colorant mobility improves, and relative humidity sensitivity reduction and zinc salt pollutant are in the minimizing of gathering fusing on device roller.Therefore described colorant is applicable to method and/or the equipment of all use colorants.

The application has solved above-mentioned and other problem, wherein the application relates to a kind of colorant in embodiments, comprise: at least one vibrin, wherein in described at least one vibrin, the amount of free polybasic acids monomer is less than 4mg/g, and M in described at least one vibrin wherein _wthe number percent that is less than 1500 vibrin is less than approximately 10% of total resin content in described colorant.

Describe in embodiments a kind of colorant, having comprised: at least one vibrin, and at least one M _wbe greater than approximately 15000 and the polydispersity index high molecular weight polyester resins that is greater than 4, in wherein said colorant, the amount of free polybasic acids monomer is less than 4mg/g, and M in described vibrin and described high molecular weight polyester resins wherein _wthe number percent that is less than 1500 vibrin is less than approximately 10% of total resin content in described colorant.

A kind of method that formation comprises the colorant of at least one vibrin has been described in other embodiments, described method comprises: at least one vibrin that is used to form described colorant is dissolved in the first solvent, use the second solvent different from described the first solvent that described at least one vibrin is precipitated out from described the first solvent, wherein said dissolving and precipitation make the acid number of described at least one vibrin reduce by 4 to 8 units to form at least one purified polyester resins, in wherein said at least one purified polyester resins, the amount of free polybasic acids monomer is less than 4mg/g, and M in described at least one purified polyester resins _wthe number percent that is less than 1500 vibrin is less than approximately 10% of total resin content in described colorant, and the vibrin of described at least one purifying is processed into pigment granules.

Embodiment

This paper describes a kind of colorant, comprising: at least one vibrin, in wherein said vibrin, the amount of free polybasic acids monomer is less than 4mg/g, and M wherein _wthe number percent that is less than described at least one vibrin of 1500 is less than approximately 10%.Described pigment granules can be by melt extruding, grind/pulverizes and the step of classification or form by for example emulsion aggregation method of chemical colorant job operation, and can have core-shell structure, be amorphous polyester resin, crystal vibrin or high molecular weight polyester resins in described core or shell or in core and shell.

Selectedly comprise for concrete vibrin of the present invention, for example, saturated and unsaturated polyester resin and/or its derivant, comprise crosslinked polyester resin, alkali sulfonated polyester resin, branching type alkali sulfonated polyester resin, crystal vibrin and amorphous polyester resin that vibrin and branching type vibrin, original position form.

The illustrative examples of the selected vibrin for method of the present invention and particle comprises any polyester, for example crystal polyester, line style and/or branching type amorphous polyester, the cross-linked polyester being formed by described line style and/or branching type amorphous polyester original position, or their potpourri.Crystal polyester comprises saturated or undersaturated polyester or their potpourri.Line style and/or branching type amorphous polyester comprise unsaturated polyester (UP), and optionally comprise saturated polyester.Therefore, for example, described pigment granules can contain the potpourri of crystal vibrin, amorphous polyester resin or two or more vibrin, and in wherein said potpourri, one or more polyester are that crystal polyester and one or more polyester are amorphous polyester.

In embodiments, described vibrin can be crystal resin." crystal " used herein refers to the polyester with three-dimensional sequence." semi-crystal resin " used herein refers to that crystal number percent is for for example approximately 10% to approximately 60%, is more preferably approximately 12% to approximately 50% resin.In addition, unless otherwise noted, " crystal vibrin " used herein and " crystal resin " comprise crystal resin and semi-crystal resin.

The illustrative examples of crystal vibrin can comprise in various crystal polyester any, for example: poly-(ethylene glycol adipate), poly-(hexane diacid propylene glycol ester), poly-(tetramethylene adipate), poly-(hexane diacid pentadiol ester), poly-(hexane diacid hexanediol ester), poly-(hexane diacid ethohexadiol ester), poly-(EGS ethylene glycol succinate), poly-(succinic acid propylene glycol ester), poly-(succinic acid-butanediol ester), poly-(succinic acid pentadiol ester), poly-(succinic acid hexanediol ester), poly-(succinic acid ethohexadiol ester), poly-(decanedioic acid glycol ester), poly-(decanedioic acid propylene glycol ester), poly-(decanedioic acid butanediol ester), poly-(decanedioic acid pentadiol ester), poly-(decanedioic acid hexanediol ester), poly-(decanedioic acid ethohexadiol ester), poly-(decanedioic acid nonanediol ester), poly-(decanedioic acid decanediol ester), poly-(decanedioic acid 11 carbon diol esters), poly-(decanedioic acid 12 carbon diol esters), poly-(dodecanedioic acid glycol ester), poly-(dodecanedioic acid propylene glycol ester), poly-(dodecanedioic acid butanediol ester), poly-(dodecanedioic acid pentadiol ester), poly-(dodecanedioic acid hexanediol ester), poly-(dodecanedioic acid ethohexadiol ester), poly-(dodecanedioic acid nonanediol ester), poly-(dodecanedioic acid decanediol ester), poly-(dodecanedioic acid 11 carbon diol esters), poly-(dodecanedioic acid 12 carbon diol esters), poly-(fumaric acid glycol ester), poly-(fumaric acid propylene glycol ester), poly-(fumaric acid butanediol ester), poly-(fumaric acid pentadiol ester), poly-(fumaric acid hexanediol ester), poly-(fumaric acid ethohexadiol ester), poly-(fumaric acid nonanediol ester), poly-(fumaric acid decanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (ethylene glycol adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (tetramethylene adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid hexanediol ester), copolymerization (5-sulfo group isophthalic diformyl-copolymerization (hexane diacid ethohexadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (ethylene glycol adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (tetramethylene adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid hexanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid ethohexadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (EGS ethylene glycol succinate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid-butanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid hexanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid ethohexadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid butanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid hexanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid ethohexadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (ethylene glycol adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (tetramethylene adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid hexanediol ester) and their potpourri.

Crystal vibrin can obtain from many sources, and they can have different fusing points, for example, from approximately 30 DEG C to approximately 120 DEG C, for example, from approximately 50 DEG C to approximately 90 DEG C.The number-average molecular weight (Mn) of crystal resin of measuring according to gel permeation chromatography (GPC) can be, for example, and from approximately 1000 to approximately 50000, preferably from approximately 2000 to approximately 25000.Use the weight-average molecular weight (M of the crystal resin of the gpc measurement of polystyrene standards _w) can be, for example, from approximately 2000 to approximately 100000, preferably from approximately 3000 to approximately 80000.The molecular weight distribution (Mw/Mn) of crystal resin can be, for example, and from approximately 2 to approximately 6, particularly from approximately 2 to approximately 4.

Described crystal resin can be prepared by the polycondensation method that suitable organic diol and suitable organic diacid are reacted under the existence of polycondensation catalyst.Conventionally, use organic diol and the organic diacid of stoichiometry equimolar ratio, but, in some cases, in the time that the boiling point of described organic diol is approximately 180 DEG C to approximately 230 DEG C, can uses excessive glycol and be removed in described polycondensation process.The amount of catalyzer used can change, and can be selected from the approximately 0.01mol% of for example described resin to about 1mol%.In addition, also can use organic diester to substitute organic diacid, now can produce alcohol accessory substance.

The example of organic diol comprises the aliphatic diol with approximately 2 to approximately 36 carbon atoms, for example, and 1,2-ethylene glycol, 1, ammediol, BDO, 1,5-PD, 1,6-hexanediol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,12-12 carbon glycol etc.; Alkali alpha-sulfonated fatty family glycol, for example, 2-sodium is for sulfo group-1, and 2-ethylene glycol, 2-lithium are for sulfo group-1,2-ethylene glycol, 2-potassio sulfo group-1,2-ethylene glycol, 2-sodium for sulfo group-1,3-PD, 2-lithium for sulfo group-1, ammediol, 2-potassio sulfo group-1,3-PD, and their potpourri etc.The approximately 45mol% that the amount of described aliphatic diol is selected from for example described resin is to about 50mol%, and the approximately 1mol% that the amount of described alkali alpha-sulfonated fatty family glycol can be selected from described resin is to about 10mol%.

Selectedly comprise ethane diacid, succinic acid, glutaric acid, hexane diacid, suberic acid, azelaic acid, decanedioic acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA), naphthalene-2 for the preparation of the organic diacid of described crystal vibrin or the example of diester, 6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexane cyclohexanedimethanodibasic, malonic acid and mesaconic acid, their diester or acid anhydrides, and alkali sulfonation organic diacid for example, the sodium of dimethyl-5-sulfoisophthalic acid, lithium or sylvite, dialkyl group-5-sulfo group isophthalic diformyl-4-sulfo group-1, 8-naphthalic anhydride, 4-sulfo group-phthalic acid, dimethyl-4-sulfo group-phthalic ester, dialkyl group-4-sulfo group-phthalic ester, 4-sulfophenyl-3, 5-bis-carbo methoxy group benzene, 6-sulfo group-2-naphthyl-3, 5-bis-carbo methoxy group benzene, sulfo group terephthalic acid (TPA), dimethyl sulfo group terephthalic acid (TPA), 5-sulfo group-m-phthalic acid, dialkyl sulfosuccinate terephthalate, sulfo group ethylene glycol, 2-sulfo group propylene glycol, 2-sulfo group butylene glycol, 3-sulfo group pentanediol, 2-sulfo group hexanediol, 3-sulfo group-2 hexylene glycol, 2-sulfo group-3, 3-dimethyl-penten glycol, sulfo group P-hydroxybenzoic acid, N, two (2-the hydroxyethyl)-Tau esters of N-, or their potpourri.The approximately 40mol% that the amount of described organic diacid is selected from for example described resin is to about 50mol%, and the approximately 1mol% that the amount of described alkali alpha-sulfonated fatty family diacid is selected from for example described resin is to about 10mol%.

Suitable crystal vibrin is included in U.S. Patent No. 7,329,476 and U.S. Patent Application Publication text No.2006/0216626,2008/0107990,2008/0236446 and 2009/0047593 in those disclosed, described every section of document is all included in herein in full by reference.In embodiments, suitable crystal resin can comprise the resin with following formula being made up of potpourri and the ethylene glycol of dodecanedioic acid and fumaric acid comonomer:

Wherein b is approximately 5 to approximately 2000, and d is approximately 5 to approximately 2000.

If use in this article semi-crystal vibrin, described semi-crystal vibrin can comprise poly-(3-methyl-1-butene), poly-(carbonic acid hexylidene ester), poly-(ethylidene-to carboxyphenoxy-butyric ester), poly-(ethylidene-vinyl acetate), poly-(acrylic acid docosyl ester), poly-(dodecylacrylate), poly-(acrylic acid stearyl), poly-(methacrylic acid stearyl), poly-(methacrylic acid docosanol polyethoxy ethyl ester), poly-(ethylene glycol adipate), poly-(hexane diacid decanediol ester), poly-(azelaic acid decanediol ester), poly-(oxalic acid hexanediol ester), poly-(oxalic acid decanediol ester), poly-(oxirane), poly-(epoxypropane), poly-(oxidation butadiene), poly-(oxidation decene), poly-(sulfuration decene), poly-(curing decene), poly-(decanedioic acid glycol ester), poly-(decanedioic acid decanediol ester), poly-(suberic acid glycol ester), poly-(succinic acid decanediol ester), poly-(malonic acid 20 carbon diol esters), poly-(to carboxyphenoxy-hendecoic acid glycol ester), poly-(two thion ethylene isophthalates) (poly (ethylenedithionesophthalate)), poly-(terephthalic acid (TPA) Propylene Glycol ester), poly-(to carboxyphenoxy-valeric acid glycol ester), poly-(the two hexyloxy benzoic acid diol esters of 4,4 '-oxo), poly-(10-hydroxydecanoic acid), poly-(m-terephthal aldehyde), poly-(dodecanedioic acid ethohexadiol ester), poly-(dimethyl siloxane), poly-(dipropyl siloxane), poly-(phenylene oxalic acid butanediol ester), poly-(three sulfo-dicarboxylic acid butanediol esters), poly-(dodecanedioic acid propylene glycol ester), poly-(m-xylene), poly-(terephthaloyl groups heptanedioyl amine) and their bond.

Described vibrin also can be line style amorphous polyester resin.The example of line style amorphous polyester resin comprises: poly-(propoxylated bisphenol-altogether-fumarate), poly-(ethoxylation bisphenol-A-altogether-fumarate), poly-(butoxy bisphenol-A-altogether-fumarate), poly-(altogether-propoxylated bisphenol-altogether-ethoxylation bisphenol-A-altogether-fumarate), poly-(fumaric acid-1,2-PD ester), poly-(propoxylated bisphenol-altogether-maleate), poly-(ethoxylation bisphenol-A-altogether-maleate), poly-(butoxy bisphenol-A-altogether-maleate), poly-(altogether-propoxylated bisphenol-altogether-ethoxylation bisphenol-A-altogether-maleate), poly-(maleic acid 1,2-PD ester), poly-(propoxylated bisphenol-altogether-itaconate), poly-(ethoxylation bisphenol-A-altogether-itaconate), poly-(butoxy bisphenol-A-altogether-itaconate), poly-(altogether-propoxylated bisphenol-altogether-ethoxylation bisphenol-A-altogether-itaconate), poly-(itaconic acid 1,2-PD ester) and their bond.

In embodiments, suitable line style amorphous polyester resin can be have following formula poly-(propoxylated bisphenol-altogether-fumarate) resin of (II):

Wherein m can be approximately 5 to approximately 100.

It is to come from Resana S/A Industrias Quimicas that an example that can be used as the line style propoxylated bisphenol fumarate resin of latex resin can be, the commodity SPARII by name of Sao Paulo Brazil ^tMresin.Other suitable line style resins are included in patent No.4, those disclosed in 533,614,4,957,774 and 4,533,614, and it can be linear polyester resin, comprises dodecyl succinic anhydride, terephthalic acid (TPA) and alkoxylate bisphenol-A.Other available commercially available propoxylated bisphenol terephthalate resins comprise can be purchased from Kao Corporation, the GTU-FC115 of Japan etc.

In embodiments, described vibrin can be saturated or undersaturated amorphous polyester resin.The illustrative examples of the selected saturated and undersaturated amorphous polyester resin for method of the present invention and particle comprises that various amorphous resins are any, for example polyethylene terephthalate, PTT, polybutylene terephthalate, poly terephthalic acid pentadiol ester, poly terephthalic acid hexanediol ester, poly terephthalic acid heptandiol ester, poly terephthalic acid ethohexadiol ester, polyethylene glycol isophthalate, poly-m-phthalic acid propylene glycol ester, poly-m-phthalic acid butanediol ester, poly-m-phthalic acid pentadiol ester, poly-m-phthalic acid hexanediol ester, poly-m-phthalic acid heptandiol ester, poly-m-phthalic acid ethohexadiol ester, polyethylene glycol sebacate, poly-decanedioic acid propylene glycol ester, polydiethylene glycol sebacate, polyethylene glycol adipate, PPA, poly adipate succinic acid ester, poly-hexane diacid pentadiol ester, poly-hexane diacid hexanediol ester, poly-hexane diacid heptandiol ester, poly-hexane diacid ethohexadiol ester, poly-EGG ethylene glycol glutarate, poly-glutaric acid propylene glycol ester, poly-glutaric acid butanediol ester, poly-glutaric acid pentadiol ester, poly-glutaric acid hexanediol ester, poly-glutaric acid heptandiol ester, poly-glutaric acid ethohexadiol ester, poly-heptandioic acid glycol ester, poly-heptandioic acid propylene glycol ester, poly-heptandioic acid butanediol ester, poly-heptandioic acid pentadiol ester, poly-heptandioic acid hexanediol ester, poly-heptandioic acid heptandiol ester, poly-(ethoxylation bisphenol-A-fumarate), poly-(ethoxylation bisphenol-A-succinate), poly-(ethoxylation bisphenol-A-adipate), poly-(ethoxylation bisphenol-A-glutarate), poly-(ethoxylation bisphenol-A-terephthalate), poly-(ethoxylation bisphenol-A-isophthalic acid ester), poly-(ethoxylation bisphenol-A-dodecenyl succinic succinate), poly-(propoxylated bisphenol-fumarate), poly-(propoxylated bisphenol-succinate), poly-(propoxylated bisphenol-adipate), poly-(propoxylated bisphenol-glutarate), poly-(propoxylated bisphenol-terephthalate), poly-(propoxylated bisphenol-isophthalic acid ester), poly-(propoxylated bisphenol-dodecenyl succinic succinate), SPAR (Dixie Chemicals), BECKOSOL (Reichhold Inc), ARAKOTE (Ciba-Geigy Corporation), HETRON (Ashland Chemical), PARAPLEX (Rohm & Haas), POLYLITE (Reichhold Inc), PLASTHALL (Rohm & Haas), CYGAL (American Cyanamide), ARMCO (Armco Composites), ARPOL (Ashland Chemical), CELANEX (Celanese Eng), RYNITE (DuPont), STYPOL (Freeman Chemical Corporation) and their bond.If necessary, described resin also can functionalised, such as carboxylic acid, sulfonated etc., and particularly for example in sodium generation, is sulfonated.

The line style obtaining from many sources or branching type amorphous resin can have different initial glass transition temperatures (Tg), for example approximately 40 DEG C to approximately 80 DEG C, for example approximately 50 DEG C to approximately 70 DEG C, described temperature records according to differential scanning calorimetry (DSC).In embodiments, described line style or branching type amorphous polyester resin can be saturated or undersaturated resin.

Line style amorphous polyester resin is conventionally by the polycondensation reaction preparation of organic diol, diacid or diester and polycondensation catalyst.Described amorphous resin is present in described colorant composition with multiple suitable amount conventionally, and for example, approximately 60 % by weight of solid or colorant are to approximately 90 % by weight, or approximately 50 % by weight are to approximately 65 % by weight.

Selectedly comprise for the preparation of the diacid of amorphous polyester or the example of diester the dicarboxylic acid or the diester that are selected from following material: terephthalic acid (TPA), phthalic acid, m-phthalic acid, fumaric acid, maleic acid, itaconic acid, succinic acid, succinic anhydride, dodecyl succinic acid, dodecyl succinic anhydride, dodecenyl succinic succinic acid, dodecenyl succinic succinic anhydride, glutaric acid, glutaric anhydride, hexane diacid, heptandioic acid, suberic acid, azelaic acid, dodecanedioic acid, dimethyl terephthalate (DMT), diethyl terephthalate, dimethyl isophthalate, dimethyl isophthalate, repefral, phthalic anhydride, diethyl phthalate, dimethyl succinate, dimethyl fumarate, dimethyl maleate, dimethyl glutarate, dimethyl adipate, dodecyl dimethyl succinate, dodecenyl succinic dimethyl succinate and their potpourri.The selected amount of described organic diacid or diester is that the approximately 45mol% of for example described resin arrives about 52mol%.The example that is used for the glycol that generates amorphous polyester comprises 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, pentanediol, hexanediol, 2, 2-dimethyl propylene glycol, 2, 2, 3-trimethyl hexanediol, heptandiol, dodecanediol, two (hydroxyethyl) bisphenol-A, two (2-hydroxypropyl) bisphenol-A, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, benzene dimethanol (xylenedimethanol), cyclohexanediol, diglycol, oxidation two (2-hydroxyethyls), dipropylene glycol, dibutene and their potpourri.The amount of selected organic diol can change, and more particularly, for example, is that the approximately 45mol% of described resin is to about 52mol%.

The example that is used for the suitable polycondensation catalyst of crystal or amorphous polyester comprises: tetraalkyl titanate, dialkyltin for example Dibutyltin oxide, tetraalkyl tin for example dibutyl tin dilaurate, dialkyltin oxyhydroxide for example Dibutyltin oxide oxyhydroxide, aluminium alkoxide, zinc alkyl, dialkyl group zinc, zinc paste, stannous oxide, or their potpourri; The selected amount of described catalyzer is for example for arriving about 5mol% for generating the initial diacid of described vibrin or the approximately 0.01mol% of diester.

Described crystal vibrin or amorphous polyester resin can be branching type resin.Term used herein " branching type " or " branching " comprise branching type resin and/or cross-linked resin.The branching agent that is used to form these branching type resins for example comprises: multivalence polyprotonic acid, as 1,2,4-benzene-tricarboxylic acids, 1,2,4-cyclohexane tricarboxylic acids, 2,5,7-naphthalene-tricarboxylic acids, 1,2,4-naphthalene-tricarboxylic acids, 1,2,5-hexane tricarboxylic acids, 1,3-dicarboxyl-2-methyl-2-methylene-carboxyl propane, four (methylene-carboxyl) methane and 1,2,7,8-octane tetrabasic carboxylic acid, their acid anhydrides and their low alkyl group (1 to approximately 6 carbon atoms) ester; Multivalent polyol is D-sorbite, 1,2 for example, and 3, the own tetrol of 6-, Isosorbide-5-Nitrae-sorbitan, pentaerythrite, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butantriol, 1,2,5-, penta triol, glycerine, 2-methyl-prop triol, 2-methyl isophthalic acid, 2,4-butantriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxy methyl benzene, their potpourri etc.The selected amount of described branching agent is for example that the approximately 0.1mol% of described resin arrives about 5mol%.

Line style or the branching type unsaturated polyester (UP) of the selected preparation of the original position for described cross-linked polyester particle and disclosure method comprise, the low-molecular-weight condensation polyester that can form by the stepwise reaction between saturated and unsaturated diacid (or acid anhydrides) and dibasic alcohol (glycol or glycol).The unsaturated polyester (UP) obtaining is reactivity (for example, crosslinkable) both ways: (i) along the unsaturated site (two key) of polyester chain and (ii) for example carboxyl, hydroxyl of functional group and can carry out the similar group of acid-base reaction.Available typical unsaturated polyester resin by melt polycondensation or other polymerizations, use diacid and/or acid anhydrides and glycol to prepare.

In embodiments, be approximately 30 DEG C to approximately 80 DEG C for the glass transition temperature of the amorphous resin of described core or the bond of amorphous resin, be approximately 35 DEG C to approximately 70 DEG C in embodiments.In other embodiments, the melt viscosity for the bond resin of described core at approximately 130 DEG C can be approximately 10 to approximately 1,000, and 000Pa*S, in embodiments, is approximately 50 to approximately 100,000Pa*S.

Unrestricted to the monomer for the preparation of selected vibrin, monomer used can comprise any or multiple of such as ethene, propylene etc.---for example dodecyl mercaptans or carbon tetrabromide---controls the molecular weight of described polyester can to use known chain transfer agents.Any appropriate method that forms described polyester by described monomer all can be used without restriction.

The amount of described vibrin can be approximately 65 % by weight of described pigment granules (that is, having got rid of the pigment granules of external adjuvant) to approximately 95 % by weight in solid, for example approximately 75 % by weight are to approximately 85 % by weight.The ratio of crystal resin and amorphous resin can be approximately 1: 99 to approximately 30: 70, for example, approximately arrive approximately 25: 75 at 5: 95.But, in embodiments, also can use amount and the ratio beyond above-mentioned scope according to the kind of other materials that exist and amount,

Can use one, two or more vibrin.In the embodiment of two or more colorant resins of use, described colorant resin can for example, exist with any suitable ratio (weight ratio), and for example approximately 10% (the first resin)/90% (the second resin) of described ratio arrives approximately 90% (the first resin)/10% (the second resin).

In embodiments, above-mentioned resin can be in conjunction with high molecular weight branched type or cross-linked resin.In embodiments, this high molecular weight resin can comprise, for example, and branching type resin or polyester, cross-linked resin or polyester or their potpourri, or carried out crosslinked non-crosslinked resin.According to the application, approximately 1 % by weight can be branching or crosslinked to the high molecular weight resin of approximately 100 % by weight, and approximately 2 % by weight can be branching or crosslinked to the high molecular weight resin of approximately 50 % by weight in embodiments.Term used herein " high molecular weight resin " refers to the weight-average molecular weight (M that dissolves in the part of chloroform according to the measured described resin of gel permeation chromatography that uses polystyrene standard control resin _w) be greater than approximately 15000 and polydispersity index (PD) resin that is greater than approximately 4.Described PD index is weight-average molecular weight (M _w) and number-average molecular weight (M _n) ratio.

High molecular weight polyester resins can be by the branching of linear polyester resin or crosslinked preparation.Can use the branching agent such as trifunctional or polyfunctional monomer, described reagent increases molecular weight and the polydispersity of described polyester conventionally.Suitable branching agent comprises glycerine, trimethylolethane, trimethylolpropane, pentaerythrite, D-sorbite, diglycerol, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic acid acid anhydride, 1,2,4-cyclohexane tricarboxylic acids, 2,5,7-naphthalene tricarboxylic acids, 1,2,4-butane tricarboxylic acids, their combination, etc.These branching agents are use amount effectively, and---arriving about 20mol% for the preparation of the initial diacid of described resin or the approximately 0.1mol% of diester---used.

Contain with the composition of the modified polyester resin that can be used for the polybasic carboxylic acid that forms macromolecule polyester resin and comprise U.S. Patent No. 3,681, those disclosed in 106, and the branching or the cross-linked polyester that are generated by polybasic acids or alcohol, as U.S. Patent No. 4,863,825,4,863,824,4,845,006,5,143,809,5,057,596,4,988,794,4,981,939,4,980,448,4,933,252,4,931,370,4,917,983 and 4, described in 973,539, the disclosure of described each section of document is all included in herein by reference.

In embodiments, crosslinked polyester resin can be prepared by the linear polyester resin that contains the unsaturated site that can react under condition of free radical.The example of described resin comprises U.S. Patent No. 5,227,460,5,376,494,5,480,756,5,500,324,5,601,960,5,629,121,5,650,484,5,750,909,6,326,119,6,358,657,6,359, those disclosed in 105 and 6,593,053, the disclosure of described each section of document is all included in herein by reference.In embodiments, suitable unsaturated polyester (UP) basis resin can, by diacid and/or acid anhydrides such as maleic anhydride, fumaric acid anhydride etc. and their combination, be prepared with glycol such as ethoxylation bisphenol-A, propoxylated bisphenol, propylene glycol etc. and their combination.In embodiments, suitable polyester is poly-(propoxylated bisphenol fumarate).

In embodiments, according to the M of the measured high molecular weight branched or crosslinked polyester resin of the GPC that uses polystyrene standard control resin _wbeing greater than approximately 15000, is approximately 15000 to approximately 1000000 in embodiments, is approximately 20000 to approximately 100000 in other embodiments; Polydispersity index (M _w/ M _n) be greater than approximately 4, be approximately 4 to approximately 100 in embodiments, be approximately 6 to approximately 50 in other embodiments.

In embodiments, crosslinked, branched polyester can be used as high molecular weight resin.This kind polyester resin can be formed by least two kinds of pregel compositions, described pregel composition comprises polyvalent alcohol or its ester that at least one has two or more hydroxyls, at least one aliphatics or aromatic series polyfunctional acid or its ester, or it has the potpourri of at least three functional groups; Optionally comprise at least one long-chain fat family carboxylic acid or its ester, or aromatic monocarboxylate or its ester, or their potpourri.Described two kinds of components can be reacted to substantially complete in different reactor, in first reactor, generate the first composition that comprises the pregel with carboxyl terminal group, in second reactor, generate the second composition that comprises the pregel with hydroxyl terminal groups.Then described two kinds of compositions can be mixed to generate crosslinked, branched polyester macromolecule amount resin.The example of the synthetic method of described polyester and they comprises U.S. Patent No. 6,592, those disclosed in 913, and the disclosure of described document is all included in herein by reference.

In embodiments, can comprise for the crosslinked, branched polyester of described high molecular weight resin those that are generated by the reaction of dimethyl terephthalate (DMT), 1,3-BDO, 1,2-PD and pentaerythrite.

Suitable polyvalent alcohol can contain has an appointment 2 to approximately 100 carbon atoms and has at least two or more hydroxyls or its ester.Polyvalent alcohol can comprise glycerine, pentaerythrite, polyglycol, polyglycerol etc., or their potpourri.Described polyvalent alcohol can comprise glycerine.Suitable glyceride comprises tripalmitin, decanedioic acid glyceride, hexane diacid glyceride, glyceryl triacetate, glyceryl tripropanoate etc.The amount of described polyvalent alcohol can be approximately 20% to approximately 30% of described reaction mixture weight, in embodiments, is approximately 20% to approximately 26% of reaction mixture weight.

There is at least aliphatics polyfunctional acid of Liang Ge functional group and can comprise saturated and unsaturated acid or its ester containing 2 to approximately 100 carbon atoms---approximately 4 to approximately 20 carbon atoms in certain embodiments---of having an appointment.Other aliphatics polyfunctional acid comprises malonic acid, succinic acid, tartrate, malic acid, citric acid, fumaric acid, glutaric acid, hexane diacid, heptandioic acid, decanedioic acid, suberic acid, azelaic acid, decanedioic acid etc., or their potpourri.Other available aliphatics polyfunctional acids comprise contains C ₃-C ₆the dicarboxylic acid of ring structure and position isomer thereof, and comprise cyclohexane dicarboxylic acid, cyclobutane dicarboxylic acid or cyclopropane dicarboxylic acid.

Available have at least the aromatic series polyfunctional acid of Liang Ge functional group comprise terephthalic acid (TPA), m-phthalic acid, trimellitic acid, pyromellitic acid and naphthalene Isosorbide-5-Nitrae-, 2,3-and 2,6-dicarboxylic acid.

Aliphatics polyfunctional acid or aromatic series polyfunctional acid's amount can be approximately 40% to approximately 65% of described reaction mixture weight, in embodiments, is approximately 44% to approximately 60% of described reaction mixture weight.

Long-chain fat family carboxylic acid or aromatic monocarboxylate can comprise described carboxylic acid or its ester containing 12 to approximately 26 carbon atoms---approximately 14 to approximately 18 carbon atoms in embodiments---of having an appointment.Long-chain fat family carboxylic acid can be saturated or undersaturated.Suitable saturated long-chain fat family carboxylic acid can comprise lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, cerinic acid etc., or their combination.Suitable unsaturated long-chain fat family carboxylic acid can comprise dodecenoic acid, palmitoleic acid, oleic acid, linoleic acid, leukotrienes, erucic acid etc., or their combination.Aromatic monocarboxylate can comprise benzoic acid, naphthoic acid and substituted naphthoic acid.Suitable substituted naphthoic acid can comprise for example 1-methyl-2-naphthoic acid of naphthoic acid and/or the 2-isopropyl-1-naphthoic acid that are replaced by the straight or branched alkyl containing 1 to approximately 6 carbon atoms of having an appointment.Described long-chain fat family's carboxylic acid or aromatic monocarboxylate's amount can be approximately 0% to approximately 70% of described reaction mixture weight, in embodiments, is approximately 15% to approximately 30% of described reaction mixture weight.

If need, also can use other polyvalent alcohols, ionic species, oligomer or their derivant.These other glycol or the amount of polyvalent alcohol can be approximately 0% to approximately 50% of described reaction mixture weight.Other polyvalent alcohol or derivatives thereof can comprise propylene glycol, 1,3-butylene glycol, 1, ammediol, 1,4-butylene glycol, 1,6-hexanediol, diglycol, 1,4-cyclohexanediol, 1,4-CHDM, neopentyl glycol, glyceryl triacetate, trimethylolpropane, pentaerythrite, cellulose ether, cellulose esters, such as cellulose acetate, sucrose acetate isobutyrate etc.

The amount of the high molecular weight resin in pigment granules of the present invention---no matter being at core or shell or in core and shell---can be approximately 1% to approximately 30% of described colorant weight, be described colorant weight approximately 2.5% to approximately 20% in embodiments, or approximately 5% to approximately 10%.

In embodiments, for example branching type polyester of described high molecular weight resin can be present on the surface of pigment granules of the present invention.The lip-deep high molecular weight resin of described pigment granules also can be particle, and the diameter of high molecular weight resin particle is that approximately 100 nanometers arrive approximately 300 nanometers, is that approximately 100 nanometers are to approximately 150 nanometers in embodiments.Described high molecular weight resin particle can cover approximately 10% to approximately 90% of described colorant surface, covers in embodiments approximately 20% to approximately 50% of described colorant surface.

In embodiments, the resin that can be used for forming shell comprises above-mentioned high molecular weight resin, and/or as above-mentioned amorphous polyester resin and the crystal vibrin of core.In embodiments, can be used for forming the amorphous of shell or crystal resin comprises amorphous polyester according to the present invention, optionally combine with above-mentioned high molecular weight resin latex.The bonding agent that multiple vibrin can be used as pigment granules combines, and amount that can any appropriate is used.In embodiments, the amount of the first amorphous polyester resin can be approximately 20 % by weight of whole shell weight resins to approximately 100 % by weight, can be in embodiments approximately 30 % by weight of whole shell weight resins to approximately 90 % by weight.Therefore, in embodiments, the amount of the second resin in shell resin can be approximately 0 % by weight of whole shell weight resins to approximately 80 % by weight, can be in embodiments approximately 10 % by weight of shell weight resin to approximately 70 % by weight.

In embodiments, each of above-mentioned vibrin (vibrin and/or high molecular weight polyester resins) is all first passed through purge process, then just adds in colorant.This process is intended to remove low molecular weight compositions from described resin, for example low molecular weight polyester resin, unreacted monomer (glycol or diacid).In addition, this process can be carried out or commercial polyester resin and high molecular weight polyester resins be carried out after forming described resin by suitable method.This purge process comprises: by heating or not heating, at least one above-mentioned vibrin is dissolved in the first solvent, use the second solvent different from the first solvent that these resins are precipitated out from the first solvent, the solubleness of wherein said vibrin in the second solvent is lower.Then can or filter and collect the resin precipitating by decant, and unnecessary solvent is removed under vacuum.Other examples of purification process comprise U.S. Patent No. 4,810, those disclosed in 775,5,004,664 and 4,523,591, and described each section of document all included in herein by reference in full.

Although purification process as herein described can at room temperature carry out, but higher treatment temperature also can be used for the method to reduce the time of dissolving described resin needs.If need at high temperature dissolve described resin, so described treatment temperature should be not higher than the boiling point of described solvent.In described settling step, lower treatment temperature can be used for accelerating this process, but lower treatment temperature can cause higher solution viscosity and therefore cause processing problem.Therefore, described method can be carried out at the temperature of approximately 5 DEG C to approximately 60 DEG C.

Processing time is depended on the combination of selected solvent, and the mixing efficiency during colorant resin properties and processing, therefore limits processing time scope normally inappropriate.If described colorant bonding agent comprises the potpourri of described vibrin, can carry out respectively above-mentioned purge process to every kind of vibrin in potpourri, or the potpourri of vibrin is carried out to above-mentioned purge process.

The case history of various dissolving methods is in U.S. Patent No. 2,762, and 788,3,935,169,4,064,079,4,591,629,5,049,647,5,478,921,5,585,460,5,756,657,5,780,520,6,087,471,6,103,774,6,241,828,6, in 369,192 and 7,368,213, described each section of document all included in herein by reference in full.The solubility parameter (SP) of the selection of the first and the second solvent based on each solvent.SP value used herein refers to the Handbook with reference to Polymer, 2 ^ndthe value that originates in the solubility parameter value of IV-341 page in Edition (J.Brandrup and E.H.Immergut, Wiley Interscience) or obtain by use Fedors method.Described SP value can be defined by following equation:

$\mathrm{SP}=\sqrt{\frac{\mathrm{\ΔE}}{V}}=\sqrt{\frac{\underset{i}{\mathrm{\Σ}}\mathrm{\Δei}}{\underset{i}{\mathrm{\Σ}}\mathrm{\Δvi}}}$

In this equation, SP represents solubility parameter, and Δ E represents cohesive energy (cal/mol), and V represents molar volume (cm ³/ mol), Δ ei represents the vaporization energy (cal/ atom or atomic group) of i atom or atomic group, Δ vi represents the molar volume (cm of i atom or atomic group ³/ atom or atomic group), i represents 1 or larger integer.

The solubility parameter of the first solvent can be approximately 8.0 to approximately 11.5, for example, and approximately 8.5 to approximately 10, approximately 8.75 to approximately 9.75 and approximately 9.00 to approximately 9.50.The solubleness of the second solvent can be below or above the above-mentioned solubility range of the first solvent, but within can not dropping on the above-mentioned solubility range of the first solvent.The right example of solvent of the first solvent and the second solvent can comprise acetone (9.8)/methyl alcohol (14.5); Methyl ethyl ketone (9.3)/ethanol (12.7); Toluene (8.9)/phenmethylol (12.1); Tetrahydrofuran (9.1)/dodecane (7.9); Methylene chloride (9.7)/ether (7.4); Methyl n-butyl ketone (8.3)/ethylene glycol (14.6); Repefral (10.7)/propyl alcohol (11.9) and 1-METHYLPYRROLIDONE (11.3)/water (23.4).Other examples can comprise for example acetone of multisolvent system (9.8)/methyl alcohol (14.5))/water (23.4); Tetrahydrofuran (9.1)/methyl ethyl ketone (9.3)/ether (7.4).Therefore, thus the first and the second solvent can be the potpourri of solvent makes its weighted mean value in conjunction with solubility parameter by as above being limited.

As discussed above, above-mentioned polyester colorant and/or high molecular weight polyesters colorant can be prepared by the progressively growth polycondensation of diacid or glycol, to form amorphous or crystal vibrin.But the monomeric substance that is used to form these polyester colorants is not combined with other monomeric substances with the amount of homogeneous.So polyester colorant comprises the polymeric material with different molecular weight, be conventionally divided into " low molecular weight substance " and " high molecular weight material ".Boundary between described " low molecular weight substance " and " high molecular weight material " conventionally and weight-average molecular weight value (M _w) relevant." low molecular weight substance " used herein is M _wbe less than and 1500 be for example less than approximately 1000, be less than approximately 750, be less than approximately 600 or be less than approximately 500 above-mentioned vibrin.

The colorant that contains these low molecular weight substances conventionally shows that powder flowbility is poor, electrification by friction is unstable and---particularly in A district (80 DEG C, 80%RH)---relative humidity sensitivity is high.Low-molecular-weight oligomer also can easily cause the proprietary cost of printer to increase due to the minimizing of fusion device average life.

Therefore above-mentioned purification process can reduce the amount of low molecular weight substance and the acid number of above-mentioned vibrin.For example, M in above-mentioned vibrin and/or high molecular weight polyester resins _wthe number percent that is less than 1500 vibrin can be less than approximately 10% of total resin content in described colorant, be less than total resin content in described colorant approximately 7.5% and be less than approximately 5% of total resin content in described colorant.Described acid number is by measuring with the vibrin that the alkali potassium hydroxide that for example N is 0.1N or NaOH titration 1g are dissolved in toluene and methanol solvent mixture.Said method can reduce by 4 to approximately 8 for example 4 to 6 units of unit by the acid number of described vibrin, thereby makes acid number and the not resin-phase ratio reduction approximately 15% to approximately 35%, approximately 20% to approximately 30% and approximately 25% to approximately 30% by said method purifying.The removal of low molecular weight acid composition is considered to make charged humidity sensitive degree to reduce, because these low molecular weight substance moisture absorptions are relatively remarkable.Even if the removal of these materials has reduced the ability of described colorant water suction and has therefore made described colorant also can keep suitable electrification by friction performance in high temperature, high humidity under (A district).In addition, because removing of low molecular weight substance almost do not affect the charged character under normal and drying condition, therefore colorant charging performance homogeneous more all under all general environment conditions.

In addition, above-mentioned purification process has also reduced the amount of free polybasic acids monomer in described vibrin and/or high molecular weight polyester resins.As mentioned above, the low molecular weight part of vibrin contains diacid composition.But, even under optimum polymerizating condition, also there is a small amount of diacid monomer not to be incorporated in described polyester, and become the free acid monomer pollutant in described vibrin.This pollutant in this article refers to free polybasic acids monomer.The acid of described free polybasic acids monomer or diacid composition can be selected from terephthalic acid (TPA), phthalic acid, m-phthalic acid, fumaric acid, maleic acid, itaconic acid, succinic acid, dodecyl succinate, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, dodecanedioic acid, oxalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid, mesaconic acid, and their potpourri.

Fusion device roller is made up of low-surface-energy elastic body conventionally, especially in order to reduce the possibility of material adhesion on described roller surface.In the time that colorant contacts with described fusion device roller, described free polybasic acids monomer reacts with multiple colorant and/or for example zinc stearate of paper additive and forms zinc salt pollutant, and it is relevant with the formation of axial bright line defect bad on final printed matter.Term used herein " axially bright line " refers to the line extending along paper axial direction that reduces printed matter overall image quality, and especially obvious in the high density of high-quality and high-definition picture, real area part.But above-mentioned purification process has reduced the amount of free polybasic acids monomer in described resin combination, thereby the formation of the gloss defect of this particular type is significantly reduced.For example, in described vibrin, the amount of free polybasic acids monomer can be less than 4mg/g resin, is less than 3.5mg/g resin, is less than 2.5mg/g resin, is less than 1.0mg/g resin, is less than 0.1mg/g resin or is less than 0.01mg/g resin.The amount of described free polybasic acids monomer can be carried out quantitative measurement or the identification by standard nuclear magnetic resonance (NMR) spectroscopic methodology and quantitatively measure by known standard items by the chromatography of ions.

The inventor also thinks, therefore the surface that the existence of described zinc salt pollutant also can increase described fusion device roller can and increase all types of polar contaminants (the fusion device oil that for example solidifies, paper dirt, colorant resin etc.), and accumulating in the lip-deep of described fusion device roller may.

Described pigment granules can be by the method preparation in any those skilled in the art's limit of power.Although described with regard to emulsion aggregation method the embodiment that pigment granules is produced below, but the appropriate method of any preparation pigment granules all can be used, comprise chemical method, for example, in U.S. Patent No. 5,290,654 and 5,302, disclosed suspension and encapsulated method in 486, the disclosure of described each section of document is all included in herein by reference.In embodiments, colorant composition and pigment granules can be by assembling and the preparation of coalescence method, the pigment granules that wherein little tree fat particle aggregation is suitable size, and then coalescence forms final pigment granules shape and form.

The average external volume particle diameter of the pigment granules obtaining can be approximately 2 to approximately 25 microns, can be approximately 3 to approximately 15 microns, or can be approximately 5 microns and arrive.In embodiments, the geometric particle size of described particle distribution (GSD) can be approximately 1.40 or lower.In other embodiments, the GSD of described pigment granules is approximately 1.25 or lower, and in other embodiments, GSD can be less than approximately 1.23.In other embodiments, the particle diameter of described particle is approximately 6 microns, and GSD is less than approximately 1.23.In certain embodiments, the particle diameter of described pigment granules is approximately 3 to approximately 12 microns.In other embodiments, the particle diameter of described pigment granules is approximately 6 microns.In other embodiments, the particle diameter of described pigment granules is approximately 5 to approximately 8.5 microns.

In embodiments, colorant composition can be prepared by emulsion aggregation method, the method for example comprising the steps: by optional colorant, optional wax and the potpourri of any other required adjuvant, with comprise above-mentioned resin and/or high molecular weight crosslinked resin---optionally as mentioned above in surfactant---emulsion aggregation, then aggregate mixture described in coalescence.Potpourri can by by colorant and optional wax or other materials---it is also optionally in the disperse phase that comprises surfactant---add in described emulsion and prepare, described emulsion can be the potpourri of two or more emulsions that contain described resin.The pH of gained potpourri can regulate by acid such as acetic acid, nitric acid etc.In embodiments, the pH of described potpourri can be adjusted to approximately 2 to approximately 5.In addition, in embodiments, can be by described mixture homogenization.If by described mixture homogenization, homogenizing can complete by turning lower mixing at per minute approximately 600 to approximately 6000.Homogenizing can comprise that for example IKA ULTRA TURRAX T50 probe homogenizer completes by any suitable mode.

After preparing said mixture, can add in described potpourri assembling reagent.Any suitable aggregating agent prepared therefrom all can be used for forming colorant.Suitable gathering reagent comprises the aqueous solution of for example bivalent cation or multivalent cation material.Described gathering reagent comprises, for example, and for example aluminium polychloride of polymerization aluminum halide (PAC), or corresponding bromide, fluoride or iodide; Aluminium silicate polymer is poly-thiosilicic acid aluminium (polyaluminum sulfosilicate, PASS) for example; Comprise aluminum chloride, aluminium nitrate, aluminium sulphate, aluminium potassium sulfate, calcium acetate, lime chloride, calcium nitrate, calcium oxalate, calcium sulphate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, cupric chloride, copper sulphate and their combination with water-soluble metal salt.In embodiments, described gathering reagent can be added in described potpourri at the temperature of the glass transition temperature lower than described resin (Tg).

Can add approximately 0.1 % by weight that the amount of the gathering reagent in the potpourri that is used to form colorant can be resin in described potpourri for example to approximately 10 % by weight, can be in embodiments approximately 0.2 % by weight to approximately 8 % by weight, in other embodiments, can be approximately 0.5 % by weight to approximately 5 % by weight.This can provide enough gathering reagent.

Can make described particle aggregation until obtain predetermined required grain size.Predetermined required size refers to forming definite required grain size that will obtain before particle, monitors grain size until reach this grain size in growth course.In growth course, can collected specimens also for example analyze mean particle size with CoulterCounter.Therefore described gathering can be by keeping high temperature, or be slowly warming up to for example approximately 40 DEG C to approximately 100 DEG C, and described potpourri is remained at this temperature to the time of approximately 0.5 hour to approximately 6 hours, approximately 1 to approximately 5 hours in embodiments, keep stirring simultaneously and carry out, described aggregated particle is provided thus.Once reach described predetermined required grain size, just stop described growth course.

Add and assemble the growth of described particle after reagent and be shaped and can under any suitable condition, complete.For example, described growth and shaping can separate under the condition of carrying out and carry out with coalescence in gathering.Assemble and the coalescence stage for distinguishing, described accumulation process can at high temperature carry out under shearing condition, and for example approximately 40 DEG C to approximately 90 DEG C, approximately 45 DEG C to approximately 80 DEG C in embodiments, described temperature can be lower than the glass transition temperature of above-mentioned resin.

Once reach the required final size of described pigment granules, just the pH of described potpourri can be adjusted to approximately 3 to approximately 10 with alkali, in embodiments approximately 5 to approximately 9.The adjusting of pH can be used for stopping stopping colorant growth.For example comprise any suitable alkali for the alkali that stops colorant growth, alkali metal hydroxide is NaOH, potassium hydroxide, ammonium hydroxide and their combination etc. such as.In embodiments, can add ethylenediamine tetraacetic acid (EDTA) to help that pH is adjusted to above-mentioned required value.

In embodiments, after gathering but before coalescence, resinous coat can be coated on the particle of gathering to form shell thereon.The above-mentioned any resin that is suitable for forming core resin all can be used as described shell.In embodiments, in described shell, can comprise above-mentioned high molecular weight resin latex.In other embodiments, above-mentioned high molecular weight resin latex can with the resin-bonded that can be used for forming described core, be then added on described particle to form shell as resinous coat.

Can described shell resin be coated on described aggregated particle by any method in those skilled in the art's limit of power.In embodiments, the resin that is used to form described shell may reside in the emulsion that comprises any above-mentioned surfactant.The emulsion of---optionally for above-mentioned high molecular weight resin latex---can form shell in conjunction with above-mentioned aggregated particle on described aggregated particle thereby to contain described resin.

When being heated to approximately 30 DEG C to approximately 80 DEG C, when the temperature of approximately 35 DEG C to approximately 70 DEG C, described shell can form on described aggregated particle in embodiments.The formation of described shell can be carried out approximately 5 minutes to approximately 10 hours, approximately 10 minutes to approximately 5 hours in embodiments.

In embodiments, the high molecular weight resin in shell resin can prevent that any crystal resin transfer in core is to described colorant surface.In addition, the resin in described shell can have lower compatibility with the crystal resin that is used to form described core, and this can cause higher colorant glass transition temperature (T _g), and therefore can improve charging characteristic and comprise A district charging characteristic.In addition, the colorant of the present invention that contains high molecular weight resin latex in core and/or shell can show excellent document offset behavior, and gloss peak reduction, be that approximately 5 Gardner's colourity gloss unit (GGU) are to about 100GGU in embodiments, be that about 10GGU is to about 80GGU in other embodiments, this can be conducive to copying of text and image, because the difference that certain user dislikes high gloss and may form between low gloss and high glaze very much.

In the time that described core or shell or core and shell comprise above-mentioned branching type high molecular weight resin, the existence of high molecular weight resin can prevent that crystal resin transfer in described core is to described colorant surface.When this may especially can occur in and have described high molecular weight resin in described shell.In addition, described shell resin can have lower compatibility with the crystal resin that is used to form described core, and this can cause higher colorant glass transition temperature (T _g), and therefore can improve stop up and charging characteristic comprise A district charging characteristic.In addition, the high molecular weight resin that is used to form core-shell particle can have and is greater than approximately 10,000,000 pool (Poise)---be greater than in embodiments approximately 50,000,000 pool---high viscosity, this can prevent that therefore any crystal resin transfer in described core from also improving A district charging performance to described colorant surface.

In embodiments, the amount that is used to form the high molecular weight resin of described core and/or shell can be approximately 2% to approximately 30% of described dry color particle weight, can be in embodiments approximately 5% to approximately 25% of described dry color particle weight.

The glass transition temperature of the above-mentioned pigment granules with the core that contains high molecular weight resin and/or shell can be approximately 30 DEG C to approximately 80 DEG C, approximately 35 DEG C to approximately 70 DEG C in embodiments.

Be focused to required grain size and applying after any optional shell, can be by described particle coalescence to required net shape, described coalescence realizes by for example following methods: described potpourri is heated to approximately 45 DEG C to approximately 100 DEG C, be heated in embodiments the temperature of approximately 55 DEG C to approximately 99 DEG C, described temperature can be or higher than the glass transition temperature of resin that is used to form described pigment granules, and/or reduction stirring rate, for example be reduced to about 100rpm to about 1000rpm, be reduced in embodiments about 200rpm to about 800rpm.Can use higher or lower temperature, should understand described temperature and depend on the resin for bonding agent.Coalescence can complete within the time of approximately 0.01 to approximately 9 hour, completes in embodiments in the time of approximately 0.1 to approximately 4 hour.

After polymerization and/or coalescence, described potpourri can be cooled to room temperature, for example approximately 20 DEG C to approximately 25 DEG C.Described cooling can carrying out rapidly or slowly as required.Suitable cooling means can comprise introduces the chuck around described reactor by cold water.After cooling, optionally available water is washed described pigment granules, then dry.Be dried and can comprise that for example freeze-drying completes by any suitable drying means.

In embodiments, being used to form colorant, wax and other adjuvants of colorant composition can be in comprising the disperse system of surfactant.In addition, pigment granules can form by emulsion aggregation method, and the resin of wherein said colorant and other compositions, in one or more surfactants, form emulsion, pigment granules gathering, coalescence, optionally washs and be dried, then recovery.

Can use one, two or more surfactants.Described surfactant can be selected from ionic surface active agent and non-ionic surfactant.Anionic surfactant and cationic surfactant are referred to as " ionic surface active agent ".In embodiments, the use amount of described surfactant can be approximately 0.01% to approximately 5% of described colorant composition weight, be for example approximately 0.75% to approximately 4% of described colorant composition weight, in embodiments, can be approximately 1% to approximately 3% of described colorant composition weight.

The example of available non-ionic surfactant comprises, for example, polyacrylic acid, methalose, methylcellulose, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, PCE, polyoxyethylene lauryl ether, polyoxyethylene Octyl Ether, NONIN HS 240, polyoxyethylene oleyl ether, polyoxyethylene 20 sorbitan monolaurate, polyoxyethylene octadecyl ether, polyoxyethylene nonylplenyl ether, dialkyl group phenoxy group gathers (ethyleneoxy) ethanol, and the IGEPAL CA-210 of Rhone-Poulenc production ^tM, IGEPAL CA-520 ^tM, IGEPAL CA-720 ^tM, IGEPAL CO-890 ^tM, IGEPAL CO-720 ^tM, IGEPALCO-290 ^tM, IGEPAL CA-210 ^tM, ANTAROX 890 ^tMwith ANTAROX 897 ^tM.Other examples of suitable non-ionic surfactant comprise the segmented copolymer of polyethylene oxide and polypropyleneoxide, comprise commercially available SYNPERONIC PE/F, are SYNPERONIC PE/F 108 in embodiments.

Available anionic surfactant comprises sulfate and sulfonate, lauryl sodium sulfate (SDS), neopelex, dodecyl naphthalene sodium sulphate, dialkyl benzene alkyl sulfate and sulfonate, and the sour colophonic acid (abitic acid) that for example can obtain from Aldrich, or the NEOGEN R that can obtain from Daiichi Kogyo Seiyaku ^tM, NEOGEN SC ^tMwith NEOGEN RK ^tM, and their combination etc.In embodiments, other suitable anionic surfactants comprise: DOWFAX ^tM2A1---a kind of alkyl diphenyl ether disulfonate (Alkyldiphenyloxide disulfonate) that comes from Dow ChemicalCompany; And/or coming from the TAYCA POWER BN2060 of Tayca Corporation (Japan), it is branched dodecylbenzene sulfonic acid sodium.The combination of these surfactants and any aforementioned anionic surfactant all can be used in embodiment.

The example of cationic surfactant---it is conventionally with positive electricity---comprising: for example, and alkyl benzyl dimethyl ammonium chloride, dialkyl benzene alkyl ammomium chloride, DTAC, alkyl benzyl ammonio methacrylate, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, brocide, C ₁₂, C ₁₅, C ₁₇the halogen of trimethylammonium bromide, quaternized polyoxy ethyl alkyl amine, dodecylbenzyl triethyl ammonium chloride, the MIRAPOL that can buy from Alkaril Chemical Company ^tMand ALKAQUAT ^tM, the SANIZOL that can buy from Kao Chemical ^tM(benzalkonium chloride) etc., and their potpourri.

In embodiments, colorant composition as herein described also can comprise colorant.Any needs or effectively colorant all can be used for described colorant composition, comprise dyestuff, pigment, their potpourri etc., as long as described colorant solubilized or be dispersed in black carrier.Can select any dyestuff or pigment, if its can be dispersed or dissolved in black carrier and with other black component compatibility.Described colorant composition can be combined with for example color index of black colorant materials (Color Index, C.I.) solvent dye, disperse dyes, modification acidity and the direct dyes of conventional colorant (modified acid and direct dye), basic-dyeable fibre, sulfur dye, vat dyestuffs etc.The example of suitable dye comprises NeozaponRed 492 (BASF), Orasol Red G (Ciba), Direct Brilliant Pink B (OrientalGiant Dyes), Direct Red 3BL (Classic Dyestuffs), Supranol Brilliant Red3BW (Bayer AG), Lemon Yellow 6G (United Chemie), Light Fast Yellow3G (Shaanxi), Aizen Spilon Yellow C-GNH (Hodogaya Chemical), Bernachrome Yellow GD Sub (Classic Dyestuffs), Cartasol BrilliantYellow 4GF (Clariant), Cibanon Yellow 2GN (Ciba), Orasol Black CN (Ciba), Savinyl Black RLSN (Clariant), Pyrazol Black BG (Clariant), Morfast Black 101 (Rohm & Haas), Diaazol Black RN (ICI), Orasol BlueGN (Ciba), Savinyl Blue GLS (Clariant), Luxol Fast Blue MBSN (PylamProducts), Sevron Blue 5GMF (Classic Dyestuffs), Basacid Blue 750 (BASF), Neozapon Black X51 (BASF), Classic Solvent Black 7 (ClassicDyestuffs), Sudan Blue 670 (C.I.61554) (BASF), Sudan Yellow 146 (C.I.12700) (BASF), Sudan Red 462 (C.I.26050) (BASF), C.I.Disperse Yellow238, Neptune Red Base NB543 (BASF, C.I.Solvent Red 49), the Neopen Blue FF-4012 of BASF, the Lampronol Black BR (C.I.Solvent Black35) of ICI, Morton Morplas Magenta 36 (C.I.Solvent Red 172), metal phthalocyanine colorant is U.S. Patent No. 6 for example, 221, those disclosed in 137, etc., the disclosure of described document is all included in herein by reference.Also can use polymeric dye, for example, as United States Patent (USP) 5, 621, 022 and 5, 231, those disclosed in 135, the disclosure of described each section of document is all included in herein by reference, described polymeric dye can be for example the Milliken Ink Yellow 869 buying from Milliken & Company, Milliken Ink Blue 92, MillikenInk Red 357, Milliken Ink Yellow 1800, Milliken Ink Black 8915-67, Reactant Orange X-38 crude product, Reactant Blue X-17 crude product, Solvent Yellow162, Acid Red 52, Solvent Blue 44 and Reactant Violet X-80 crude product.

Pigment is also the colorant that is applicable to described colorant China ink.The example of suitable pigments comprises PALIOGEN Violet 5100 (can buy from BASF); PALIOGEN Violet 5890 (can buy from BASF); HELIOGEN Green L8730 (can buy from BASF); LITHOLScarlet D3700 (can buy from BASF); SUNFAST Blue 15:4 (can buy from Sun Chemical); Hostaperm Blue B2G-D (can buy from Clariant); Hostaperm BlueB4G (can buy from Clariant); Permanent Red P-F7RK; Hostaperm Violet BL (can buy from Clariant); LITHOL Scarlet 4440 (can buy from BASF); Bon RedC (can buy from Dominion Color Company); ORACET Pink RF (can buy from Ciba); PALIOGEN Red 3871 K (can buy from BASF); SUNFAST Blue 15:3 (can buy from Sun Chemical); PALIOGEN Red 3340 (can buy from BASF); SUNFAST Carbazole Violet 23 (can buy from Sun Chemical); LITHOL FastScarlet L4300 (can buy from BASF); SUNBRITE Yellow 17 (can buy from SunChemical); HELIOGEN Blue L6900, L7020 (can buy from BASF); SUNBRITE Yellow 74 (can buy from Sun Chemical); SPECTRA PAC COrange 16 (can buy from Sun Chemical); HELIOGEN Blue K6902, K6910 (can buy from BASF); SUNFAST Magenta 122 (can buy from Sun Chemical); HELIOGEN Blue D6840, D7080 (can buy from BASF); Sudan Blue OS (can buy from BASF); NEOPEN Blue FF4012 (can buy from BASF); PV Fast BlueB2GO1 (can buy from Clariant); IRGALITE Blue BCA (can buy from Ciba); PALIOGEN Blue 6470 (can buy from BASF); Sudan Orange G (can buy from Aldrich), Sudan Orange 220 (can buy from BASF); PALIOGEN Orange 3040 (BASF); PALIOGEN Yellow 152,1560 (can buy from BASF); LITHOL FastYellow 0991 K (can buy from BASF); PALIOTOL Yellow 1840 (can buy from BASF); NOVOPERM Yellow FGL (can buy from Clariant); Ink Jet Yellow 4GVP2532 (can buy from Clariant); Toner Yellow HG (can buy from Clariant); Lumogen Yellow D0790 (can buy from BASF); Suco-Yellow L1250 (can buy from BASF); Suco-Yellow D1355 (can buy from BASF); Suco Fast Yellow Dl355, Dl 351 (can buy from BASF); HOSTAPERM Pink E 02 (can buy from Clariant); Hansa Brilliant Yellow 5GX03 (can buy from Clariant); PermanentYellow GRL 02 (can buy from Clariant); Permanent Rubine L6B 05 (can buy from Clariant); FANAL Pink D4830 (can buy from BASF); CINQUASIAMagenta (can buy from DU PONT); PALIOGEN Black L0084 (can buy from BASF); Pigment Black K801 (can buy from BASF); And such as REGAL330TM of carbon black (can buy from Cabot), Nipex 150 (can buy from Degusssa), Carbon Black5250 and Carbon Black 5750 (can buy from Columbia Chemical) etc., and their potpourri.

U.S. Patent No. 6, 472, 523, U.S. Patent No. 6, 726, 755, U.S. Patent No. 6, 476, 219, U.S. Patent No. 6, 576, 747, U.S. Patent No. 6, 713, 614, U.S. Patent No. 6, 663, 703, U.S. Patent No. 6, 755, 902, U.S. Patent No. 6, 590, 082, U.S. Patent No. 6, 696, 552, U.S. Patent No. 6, 576, 748, U.S. Patent No. 6, 646, 111, U.S. Patent No. 6, 673, 139, U.S. Patent No. 6, 958, 406, U.S. Patent No. 6, 821, 327, U.S. Patent No. 7, 053, 227, United States Patent (USP) 7, 381, 831 and United States Patent (USP) 7, 427, in 323, disclosed colorant is also suitable for, the disclosure of described each section is all included in herein by reference.

In embodiments, use solvent dye.The example that is applicable to solvent dye herein comprises alcohol (spirit) soluble dye, because they are compatible with black carrier disclosed herein.The example of suitable alcoholic solvent dyestuff comprises Neozapon Red 492 (BASF); Orasol Red G (Ciba); Direct Brilliant Pink B (Global Colors); Aizen Spilon Red C-BH (Hodogaya Chemical); Kayanol Red 3BL (Nippon Kayaku); Spirit FastYellow 3G; Aizen Spilon Yellow C-GNH (Hodogaya Chemical); CartasolBrilliant Yellow 4GF (Clariant); Pergasol Yellow CGP (Ciba); OrasolBlack RLP (Ciba); Savinyl Black RLS (Clariant); Morfast Black Conc.A (Rohm and Haas); Orasol Blue GN (Ciba); Savinyl Blue GLS (Sandoz); Luxol Fast Blue MBSN (Pylam); Sevron Blue 5GMF (Classic Dyestuffs); Basacid Blue 750 (BASF), Neozapon Black X51[C.I.Solvent Black, C.I.12195] (BASF), Sudan Blue 670[C.I.61554] (BASF), Sudan Yellow 146[C.I.12700] (BASF), Sudan Red 462[C.I.260501] (BASF), their potpourri etc.

Described colorant can any needs or effectively amount be present in described colorant to obtain required color or tone, for example described China ink of described amount at least about 0.1 % by weight to approximately 50 % by weight, described China ink at least about 0.2 % by weight to approximately 20 % by weight, and described China ink at least about 0.5 % by weight to approximately 10 % by weight.

Optionally, wax also can be used to form described pigment granules jointly with resin and colorant.In the time containing wax in colorant, the content of wax can be approximately 1 % by weight of for example described pigment granules to approximately 25 % by weight, is that approximately 5 % by weight of described pigment granules are to approximately 20 % by weight in embodiments.

Selectable wax comprises that for example weight-average molecular weight is approximately 500 to approximately 20000 wax, is approximately 1000 to approximately 10000 wax in embodiment.Available wax comprises, for example, polyolefin is tygon, polypropylene and polybutylene wax for example---for example can buy from Allied Chemical and PetroliteCorporation, for example come from Baker Petrolite POLYWAX Tissuemat E, can be from Michaelman, the wax emulsion of Inc. buying with Daniels Products Company, can be from Eastman Chemical Products, Inc. the EPOLENE N-15 buying, and the lower molecular wt polypropylene VISCOL 550-P that can buy from Sanyo Kasei K.K.; Vegetable wax, for example palm wax, rice bran wax, candelila wax, sumac wax (sumacs wax) and jojoba oil; Animal wax, for example beeswax; Mineral wax and pertroleum wax, for example montan wax, ceresine, ceresin (ceresin), paraffin, microcrystalline wax and Fischer-Tropsch wax; The ester type waxes obtaining from higher fatty acid and higher alcohol, for example stearic acid stearyl and docosanoic acid docosyl ester; The ester type waxes obtaining from higher fatty acid and unit price or multivalence lower alcohol, for example butyl stearate, oleic acid propyl ester, glycerin monostearate, distearin and four behenic acid pentaerythritol esters; The ester type waxes obtaining from higher fatty acid and multivalence alcohol polymer, for example monostearate diglycol ester, distearyl acid dipropylene glycol ester, distearyl acid two glyceride and four glycerol stearates; Anhydro sorbitol higher fatty acid ester type waxes, for example monostearate Isosorbide Dinitrate, and cholesterol higher fatty acid ester type waxes, for example stearic acid cholesteryl ester.The example of available functionalized waxes comprises, for example, and amine; Acid amides, the AQUA SUPERSLIP 6550 that for example can obtain from Micro PowderInc., SUPERSLIP 6530; Fluoridize wax, POLYFLUO 190, POLYFLUO 200, POLYSILK 19, the POLYSILK 14 that for example can obtain from Micro Powder Inc.; The amide waxe of mixed fluoride, the MICROSPERSION 19 that for example also can obtain from MicroPowder Inc.; Diimide; Ester; Quaternary amine; Carboxylic acid; Or acrylate polymer emulsion, the JONCRYL 74,89,130,537 and 538 that for example can obtain from SC Johnson Wax; And chlorinated polypropylene and the tygon that can obtain from Allied Chemical and Petrolite Corporation, and SC Johnson wax.The potpourri of above-mentioned wax and bond also can be used in embodiment.Institute's content of wax can be used as for example fusing device roller release agent.

Pigment granules of the present invention optionally can be by mixing described pigment granules to make developer composition with carrier granular.The illustrative examples that can be selected to the carrier granular mixing with the colorant composition of preparing according to the present invention comprises and can obtain and those particles of the electric charge of described pigment granules opposite polarity by electrification by friction.Therefore, in one embodiment, can select described carrier granular so that it is electronegative, thereby make the pigment granules of positively charged can adhere to and surround described carrier granular.The illustrative examples of this class carrier granular comprises iron, ferroalloy, and steel, nickel, ferrite (iron ferrite) comprises the ferrite that contains strontium, magnesium, manganese, copper, zinc etc., magnet etc.In addition, what can be elected to be carrier granular has a U.S. Patent No. 3,847, disclosed Nickel Berry carrier in 604, the knot shape carrier globule that it comprises nickel, be characterised in that depression and projection come across surface repeatedly and thus for particle provides sizable external area, the disclosure of above-mentioned document is all included in herein by reference.U.S. Patent No. 4,937, discloses other carriers in 166 and 4,935,326, and the disclosure of described document is all included in herein by reference.

Selected carrier granular can with or without coating use, and described coating contains following material conventionally: acrylic acid and methacrylate polymer, for example methyl methacrylate; The acrylic acid and the methacrylic acid copolymer that form with fluoropolymer or with monoalkyl or dialkylamine; Fluoropolymer; Polyolefin, polystyrene, for example poly-inclined to one side vinylidene fluoride resin, cinnamic trimer, methyl methacrylate and silane, for example triethoxysilane, tetrafluoroethene, other known coating etc.

Described carrier granular can mix with various suitable combining form with described pigment granules.Described colorant content is generally the carrier of approximately 2 % by weight to the colorant of approximately 10 % by weight and approximately 90 % by weight to approximately 98 % by weight.But, also can use different colorants and carrier number percent to obtain the developer composition with desirable characteristics.

Colorant of the present invention can be used for xerography (comprising electrofax) imaging method.Therefore, for example, developer of the present invention or colorant can be for example by electrification by friction and charged, and can be applied to the sub-image with opposite charges on for example photoreceptor on image-forming component or ionic spectrum receptacle.Then can be by gained toner image directly or transfer on for example paper of holder or transparent membrane by transfer element.Then can make toner image and holder fusion by for example heating by modes such as heat fusion device rollers and/or pressurizeing.

Can be contemplated to, colorant of the present invention can be used for forming with colorant any appropriate method of image, comprises xeroprinting application application in addition.

Below provided embodiment, its example has illustrated and can be used for implementing different components of the present invention and condition.Unless otherwise noted, all ratios are all weight ratio.But clearly, the present invention can implement by the composition of multiple types, and can there is multiple different application according to disclosure and content as indicated below above.

Described colorant can be used for electrophotographic image forming or electrostatic printing method, is included in U.S. Patent No. 4,295, in 990 disclosed those, described document is included in herein by reference in full.In embodiments, the toning system of any known type all can be used for developing apparatus, described system comprises that for example magnetic brush development, transition single part develop (jumping single-componentdevelopment), mixes and exempt from removing formula development (hybrid scavengeless development, HSD) etc.These and similar toning system are within those skilled in the art's limit of power.

Formation method comprises for example uses electrostatic printing apparatus imaging, and described equipment comprises charging unit, image-forming block, photoconductive components, developing parts, transfering part and fusion parts.In embodiments, described developing parts can comprise by carrier is mixed to the developer of preparing with colorant composition as herein described.Described electrostatic printing apparatus can comprise high-speed printer (HSP), black and white high-speed printer (HSP), color printer etc.

Once with colorant/developer by any formation image of for example said method of suitable developing method, just can be by described image transfer to the image receptor medium such as such as paper.In embodiments, described colorant is used in the developing apparatus that uses fusion device roller element and shows image.Fusion device roller element contact fusing apparatus known to those skilled in the art, wherein can be used for described colorant to be fused on described image receptor medium from heat and the pressure of described roller.In embodiments, be fused to image receive in matrix after or during, described fuser member can be heated above to the temperature of the fusion temperature of described colorant, for example be heated to approximately 70 DEG C to approximately 160 DEG C, approximately 80 DEG C to approximately 150 DEG C in embodiments, approximately 90 DEG C to approximately 140 DEG C in other embodiments.

embodiment

resin emulsion preparation

resin embodiment 1

In 500ml beaker, inject 300g MEK (MEK).In stirring described MEK solution with the rotating speed of 256rpm, slowly add 200g Resin A (polycondensation product of 1: 1 potpourri of terephthalic acid (TPA) and ethoxylation bisphenol-A and propoxylated bisphenol), then continue to stir until obtain settled solution.Then under the mechanical raking of 350rpm, this solution is slowly added in the 750g methyl alcohol in 2L beaker.Above-mentioned add for the second time after, gained potpourri is stirred 2 hours again, the gained of then collecting purified resin by filtration precipitates to remove excessive solvent, and further dry under 40 DEG C, vacuum condition.

resin comparative examples 1

Resin for resin comparative examples 1 is identical with the resin (Resin A) for resin embodiment 1, except the resin for resin comparative examples 1 is processed without the purification process described in resin embodiment 1.

resin embodiment 2-4

With with resin embodiment 1 in identical method prepare resin embodiment 2-4, except use respectively the Resin A of resin B, resin C and resin D instead of resins embodiment 1 in resin embodiment 2-4.Resin B is made up of the polycondensation product (seeing formula II above) of propoxylated bisphenol and fumaric acid.Resin C is the cross-linked form of resin B, and as U.S. Patent No. 5,227, described in 460, described document is included in herein by reference in full.Resin D is by the polycondensation product of 1: 1 potpourri of terephthalic acid (TPA) and ethoxylation bisphenol-A and propoxylated bisphenol and in conjunction with forming using a small amount of trimellitic acid as branching agent.

resin comparative examples 2-4

Be used for the resin of resin comparative examples 2-4 respectively with identical for the resin of resin embodiment 2-4, except the resin for resin comparative examples 2-4 is without the processing of the purification process described in resin embodiment 1 above.

analyze: resin embodiment 1-4 and resin comparative examples 1-4

Usable range is at 590-841, the polystyrene standards of 700g/mol, with can be from PolymerLaboratories (Varian, Inc.) the 2 PL Mixed-C posts that obtain, can, from the instrument that ShimadzuScientific Instruments Corporation obtains, measure the molecular weight of polyesters of resin embodiment 1-4 and resin comparative examples 1-4 by the gel permeation chromatography (GPC) of chloroform soluble solution part (0.2 μ m membrane filtration).Automatically calculate M by the software that can obtain from Polymer Laboratories _n, M _p, M _wand M _zvalue.Every kind of polyester sample is calculated to the relative quantity that is used as high molecular and low-molecular-weight resin above and below the relative index of refraction response factor of 1500 mass units.By measure the acid number of resin in resin embodiment 1-4 and resin comparative examples 1-4 with every kind of resin of potassium hydroxide (KOH) titration.Use the calibrator quantity of known standard items, measure the amount of fumaric acid and terephthalic acid units with chromatography of ions (IC).Each of these values is all shown in table 1 below and table 2.

table 1

Resin	Resin kind	Acid number (mg KOH/g)	Fumaric acid that IC surveys (μ g/g)	Terephthalic acid (TPA) that IC surveys (μ g/g)	M n	M p	M w	M z
									Embodiment 1	A	14.1	1200	1400	4852	6140	7546	11574
Comparative example 1	A	21.0	4600	1600	4794	6423	7654	11924
									Embodiment 2	B	11.5	3900	＜2	6198	7327	13163	34650
Comparative example 2	B	16.3	17000	62	6077	7885	13955	38276
									Embodiment 3	C	11.3	2100	＜2	6345	6671	21265	160442
Comparative example 3	C	17.8	15000	＜10	5598	6610	18282	124892
									Embodiment 4	D	22.3	＜2	170	7129	7248	38393	534108
Comparative example 4	D	31.8	79	1300	6721	7579	24492	103508

table 2

Resin	Polydispersity (M w/M n)	M wBe greater than 1500 daltonian resin %	M wBe less than 1500 daltonian resin %
				Embodiment 1	1.56	90.5	9.5
Comparative example 1	1.60	84.9	15.1
				Embodiment 2	2.12	96.0	4.0
Comparative example 2	2.30	90.9	9.1
				Embodiment 3	3.35	97.3	2.7
Comparative example 3	3.27	87.8	12.2
				Embodiment 4	5.39	92.8	7.2
Comparative example 4	3.64	88.1	11.9

As shown in Table 1, the acid number of the purifying resin of resin embodiment 1-4 is than the low 4-6 unit of not purifying resin of resin comparative examples 1-4.This shows that low-molecular-weight acids material (conventionally poor relevant with electric charge control under the wet condition causing that absorbs water due to colorant) is removed.This conclusion is by minimizing (table 1) and the M of the amount of fumaric acid and terephthalic acid (TPA) pollutant _wthe number percent that is less than 1500 daltonian resins declines by (table 2) and is confirmed.

colorant preparation

colorant embodiment 1

By the purifying Resin A of preparing according to resin embodiment 1 by 55 parts, 40 parts of purifying resin D that prepare according to resin embodiment 4, and the potpourri of 5 parts of carbon blacks composition is by roll premix 20 minutes of cylinder.Then use double screw extrusion machine by this potpourri melt kneading.Then by adding the granule silicon dioxide grinding aid of 0.3 % by weight by extrudate micronization, making volume intermediate value target is 7.6 microns, and then classification is to remove particulate, and making volume intermediate value target is 8.3 microns.By original colorant and granule, carry out surface additive through the pyrogenic silica of hydrophobic treatments and titania and zinc stearate and mix, as U.S. Patent No. 6,365, described in 316 embodiment 9, described document is included in herein by reference in full.As last step, colorant is sieved to remove bulky grain.

colorant comparative example 1

With with colorant embodiment 1 in identical method prepare colorant comparative example 1, except substituting resin used in colorant embodiment 1 with the not purifying resin in resin comparative examples 1 and resin comparative examples 4 respectively.

colorant embodiment 2

By 71 parts of purifying resin B of preparing according to resin embodiment 2,24 parts of purifying resin C that prepare according to resin embodiment 3, and the potpourri of 5 parts of carbon blacks is by roll premix 20 minutes of cylinder.Then use double screw extrusion machine by this potpourri melt kneading.Then by adding the granule silicon dioxide grinding aid of 0.3 % by weight by extrudate micronization, making volume intermediate value target is 7.6 microns, and then classification is to remove particulate, and making volume intermediate value target is 8.3 microns.By original colorant and granule, carry out surface additive through the pyrogenic silica of hydrophobic treatments and titania and zinc stearate and mix, as U.S. Patent No. 6,365, described in 316 embodiment 9, described document is included in herein by reference in full.As final step, colorant is sieved to remove bulky grain.

colorant comparative example 2

With with colorant embodiment 2 in identical method prepare colorant comparative example 2, except substituting resin used in colorant embodiment 2 with the not purifying resin in resin comparative examples 2 and resin comparative examples 3 respectively.

As mentioned above, measure the molecular weight of polyesters of the resin in colorant embodiment 1-2 and resin comparative examples 1-2 by gel permeation chromatography (GPC).These the results are shown in following table 3.

The physical property that detects the various colorants of colorant embodiment 1-2 and colorant comparative example 1-2, the results are shown in following table 3.

table 3

Colorant	Resin kind	Fumaric acid that IC surveys (μ g/g)	Terephthalic acid (TPA) that IC surveys (μ g/g)	M n	M p	M w	M z	Polydispersity (M w/M n)
									Embodiment 1	A/D	860	1100	3197	6353	15334	163593	4.80
Comparative example 1	A/D	690	1700	2474	6353	9981	43752	4.00
									Embodiment 2	B/C	2600	＜2	4499	7208	12295	32534	2.73
Comparative example 2	B/C	4500	6.2	3196	7280	11495	33609	3.60

table 4

Colorant	M wBe greater than 1500 daltonian resin %	M wBe less than 1500 daltonian resin %
			Embodiment 1	91.1	8.9
Comparative example 1	85.9	14.1
			Embodiment 2	95.1	4.9
Comparative example 2	89.7	10.3

As shown in table 3 above and 4, M in the amount of fumaric acid monomer and terephthalic acid monomers and colorant _wthe number percent that is less than 1500 daltonian resins all declines to some extent.These evidences have further confirmed just from described resin, to have removed undesired low molecular weight substance before joining described colorant.

developer preparation

By the colorant embodiment 1-2 of about 4g and colorant comparative example 1-2 and about 100g being coated with to carrier (65 microns of steel cores of approximately 1 % by weight polymethylmethacrylate, HoeganaesCorporation) combine and prepare developer, then measuring the charging characteristic of described developer.By described developer paint shaker (Red Devil 5400, be adjusted to 600 and 650RPM between move) in violent mixing 10 minutes.The method is considered to simulate and inputs for the identical mechanical energy to pigment granules of the mechanical energy input in bad border of xeroprinting shell with low colorant flux mode,, xeroprinting shell produces following a kind of printed matter, approximately 0% of described printed matter to approximately 2% is covered approximately 100 to approximately 10000 impressions by the colorant developing from this shell.Developer (developer 1-2 and contrast developer 1-2) under the condition in Dui Sange district---A district (80 °F/80%RH), B district (70 °F/50%RH) and J district (70 °F/10%RH)---has been measured its static charge.These the results are shown in following table 5.

table 5

Developer	Resin	The A-10min that rubs	The B-10min that rubs	The J-10min that rubs	J/A 10 min	J/B 10 min
							Embodiment 1	A/D	20.84	44.10	63.71	3.06	1.44
Comparative example 1	A/D	14.42	42.33	65.90	4.57	1.56
							Embodiment 2	B/C	18.69	41.14	58.82	3.15	1.43
Comparative example 2	B/C	10.61	37.44	55.80	5.26	1.49

As above shown in table 5, developer 1 and 2 (the colorant resin that contains purifying) has much higher static charge in A district.In machine, this will provide much consistent printed matter under very wide in range environmental baseline, even and if also still make the control of printer become simpler under the indoor conditions changing.

colorant printing embodiment

Use the colorant described in colorant embodiment 2 and colorant comparative example 2, on 120gsm XeroxDigital Color Elite Gloss paper, on standard testing document, print 25000 images.Use FTIR spectral analysis, to these picture appraisals of printing by for example relative extent that gather the fusion device roller surface contamination that cause of zinc fumarate on fusion device roller of zinc salt.By the relative absorption intensity with respect to known calibration standard items under important wavelength, use FTIR spectral analysis to measure the relative quantity that is deposited on the pollutant that fuses device roller surface.Following table 6 shows the result of this analysis.

table 6

Colorant	Resin	Diacid zinc surface coverage rate %	Viton surface coverage %	Resin surface coverage rate %
					Embodiment 2	B/C	0.61	97.4	0.26
Comparative example 2	B/C	0.82	97.2	0.36

As above shown in table 6, the fusion device roller of colorant embodiment 1 pollutes lower, because the diacid zinc surface coverage rate on (1) fusion device roller declines to some extent compared with the colorant of colorant comparative example 1 and the increase of (2) Viton surface coverage.The Viton surface coverage of brand-new fusion device roller is 100%.In addition, the surface coverage of the colorant in colorant embodiment on fusion device roller declines to some extent.

Should be understood that disclosed and other various features and function above, or their alternative features and function, can be combined into as required many other different systems or application.Meanwhile, can make current unpredictable or the various replacement schemes, transformation, modification or the improvement that expect after those skilled in the art, below claim be also intended to comprise these contents.

Claims (10)

1. a colorant, comprising:

At least one purified polyester resins,

In wherein said at least one purified polyester resins, the amount of free polybasic acids monomer is lower than 4mg/g,

The number percent that in wherein said at least one purified polyester resins, Mw is less than 1500 polyester is less than 10% of total resin content in described colorant, and

The acid number of wherein said at least one purified polyester resins reduces by 15% to 35% compared with unpurified this vibrin, the reduction of this acid number is by described at least one vibrin is dissolved in the first solvent, and the use the second solvent different from the first solvent is precipitated out described at least one vibrin from the first solvent.

2. the colorant of claim 1, wherein said at least one purified polyester resins is amorphous polyester resin, crystal vibrin or their bond.

3. the colorant of claim 2, wherein said amorphous polyester resin comprises the polyester that is selected from following material: polyethylene terephthalate, PTT, polybutylene terephthalate, poly terephthalic acid pentadiol ester, poly terephthalic acid hexanediol ester, poly terephthalic acid heptandiol ester, poly terephthalic acid ethohexadiol ester, polyethylene glycol isophthalate, poly-m-phthalic acid propylene glycol ester, poly-m-phthalic acid butanediol ester, poly-m-phthalic acid pentadiol ester, poly-m-phthalic acid hexanediol ester, poly-m-phthalic acid heptandiol ester, poly-m-phthalic acid ethohexadiol ester, polyethylene glycol sebacate, poly-decanedioic acid propylene glycol ester, polydiethylene glycol sebacate, polyethylene glycol adipate, PPA, poly adipate succinic acid ester, poly-hexane diacid pentadiol ester, poly-hexane diacid hexanediol ester, poly-hexane diacid heptandiol ester, poly-hexane diacid ethohexadiol ester, poly-EGG ethylene glycol glutarate, poly-glutaric acid propylene glycol ester, poly-glutaric acid butanediol ester, poly-glutaric acid pentadiol ester, poly-glutaric acid hexanediol ester, poly-glutaric acid heptandiol ester, poly-glutaric acid ethohexadiol ester, poly-heptandioic acid glycol ester, poly-heptandioic acid propylene glycol ester, poly-heptandioic acid butanediol ester, poly-heptandioic acid pentadiol ester, poly-heptandioic acid hexanediol ester, poly-heptandioic acid heptandiol ester, poly-(ethoxylation bisphenol-A-fumarate), poly-(ethoxylation bisphenol-A-succinate), poly-(ethoxylation bisphenol-A-adipate), poly-(ethoxylation bisphenol-A-glutarate), poly-(ethoxylation bisphenol-A-terephthalate), poly-(ethoxylation bisphenol-A-isophthalic acid ester), poly-(ethoxylation bisphenol-A-dodecenyl succinic succinate), poly-(propoxylated bisphenol-fumarate), poly-(propoxylated bisphenol-succinate), poly-(propoxylated bisphenol-adipate), poly-(propoxylated bisphenol-glutarate), poly-(propoxylated bisphenol-terephthalate), poly-(propoxylated bisphenol-isophthalic acid ester), poly-(propoxylated bisphenol-dodecenyl succinic succinate) and their bond.

4. the colorant of claim 2, wherein said crystal vibrin comprises the polyester that is selected from following material: poly-(ethylene glycol adipate), poly-(hexane diacid propylene glycol ester), poly-(tetramethylene adipate), poly-(hexane diacid pentadiol ester), poly-(hexane diacid hexanediol ester), poly-(hexane diacid ethohexadiol ester), poly-(EGS ethylene glycol succinate), poly-(succinic acid propylene glycol ester), poly-(succinic acid-butanediol ester), poly-(succinic acid pentadiol ester), poly-(succinic acid hexanediol ester), poly-(succinic acid ethohexadiol ester), poly-(decanedioic acid glycol ester), poly-(decanedioic acid propylene glycol ester), poly-(decanedioic acid butanediol ester), poly-(decanedioic acid pentadiol ester), poly-(decanedioic acid hexanediol ester), poly-(decanedioic acid ethohexadiol ester), poly-(decanedioic acid nonanediol ester), poly-(decanedioic acid decanediol ester), poly-(decanedioic acid 11 carbon diol esters), poly-(decanedioic acid 12 carbon diol esters), poly-(dodecanedioic acid glycol ester), poly-(dodecanedioic acid propylene glycol ester), poly-(dodecanedioic acid butanediol ester), poly-(dodecanedioic acid pentadiol ester), poly-(dodecanedioic acid hexanediol ester), poly-(dodecanedioic acid ethohexadiol ester), poly-(dodecanedioic acid nonanediol ester), poly-(dodecanedioic acid decanediol ester), poly-(dodecanedioic acid 11 carbon diol esters), poly-(dodecanedioic acid 12 carbon diol esters), poly-(fumaric acid glycol ester), poly-(fumaric acid propylene glycol ester), poly-(fumaric acid butanediol ester), poly-(fumaric acid pentadiol ester), poly-(fumaric acid hexanediol ester), poly-(fumaric acid ethohexadiol ester), poly-(fumaric acid nonanediol ester), poly-(fumaric acid decanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (ethylene glycol adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (tetramethylene adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid hexanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid ethohexadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (ethylene glycol adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (tetramethylene adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid hexanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid ethohexadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (EGS ethylene glycol succinate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid-butanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid hexanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (succinic acid ethohexadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid butanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid hexanediol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (decanedioic acid ethohexadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (ethylene glycol adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid propylene glycol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (tetramethylene adipate), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid pentadiol ester), copolymerization (5-sulfo group isophthalic diformyl)-copolymerization (hexane diacid hexanediol ester) and their potpourri.

5. the colorant of claim 1, the acid constituents of wherein said free polybasic acids monomer is selected from terephthalic acid (TPA), phthalic acid, m-phthalic acid, fumaric acid, maleic acid, itaconic acid, succinic acid, dodecyl succinate, dodecenyl succinic succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, dodecanedioic acid, oxalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid, mesaconic acid, and their potpourri.

6. the colorant of claim 1, the acid constituents of wherein said free polybasic acids monomer is fumaric acid.

7. the colorant of claim 1, wherein said colorant also comprises one or more optional members, described optional member is selected from: colorant, wax and their bond.

8. the colorant of claim 1, the number percent that wherein Mw is less than at least one polyester of 1500 is less than 7.5%.

9. a colorant, comprising:

At least one purified polyester resins, and

At least one Mw is greater than 15000 and the polydispersity index purification of high molecular weight vibrin that is greater than 4,

In wherein said colorant, the amount of free polybasic acids monomer is lower than 4mg/g,

The number percent that in wherein said purified polyester resins and purification of high molecular weight vibrin, Mw is less than 1500 polyester is less than 10% of total resin content in described colorant, and

The acid number of wherein said at least one purified polyester resins reduces by 15% to 35% compared with unpurified this vibrin, the reduction of this acid number is by described at least one vibrin is dissolved in the first solvent, and the use the second solvent different from the first solvent is precipitated out described at least one vibrin from the first solvent.

10. a method for the colorant that formation contains at least one purified polyester resins, described method comprises:

At least one vibrin is dissolved in the first solvent, uses the second solvent different from described the first solvent that described at least one vibrin is precipitated out from described the first solvent,

Wherein said dissolving and precipitation make the acid number of described at least one vibrin reduce by 4 to 8 units to form at least one purified polyester resins, in wherein said at least one purified polyester resins, the amount of free polybasic acids monomer is less than 4mg/g, and the number percent that in described at least one purified polyester resins, Mw is less than 1500 polyester is lower than 10% of total resin content in described colorant, and the acid number of wherein said at least one purified polyester resins reduces by 15% to 35% compared with unpurified this vibrin, and

The vibrin of described at least one purifying is processed into pigment granules,

Wherein the solubility parameter of the first solvent is 8.0 to 11.5; The solubleness of the second solvent can be below or above the above-mentioned solubility range of the first solvent, but within can not dropping on the above-mentioned solubility range of the first solvent.